炭基载体含氧基团对Mn-Ce双金属吸附剂脱硫活性的影响
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摘要
以无烟煤、烟煤、褐煤以及工业半焦、烟煤半焦为载体,采用超声辅助加压浸渍法制备了Mn-Ce双金属吸附剂。利用固定床装置对吸附剂的烟气脱硫活性进行了评价,并运用BET、XRD和FTIR技术对其进行了表征。结果表明:吸附剂的脱硫活性主要由焙烧后的金属氧化物提供,金属离子本身无脱硫活性;炭基载体中的酯基是影响金属组分脱硫活性的主要因素,酯基在焙烧过程中分解使得金属组分暴露出来,提高了吸附剂的脱硫活性;中等变质程度的烟煤是制备吸附剂的良好载体,含有适量酯基,使得吸附剂表面金属组分分散均匀。
Mn-Ce bimetallic adsorbents were prepared by ultrasonic assisted pressure impregnation process using carbon-based carriers of anthracite coal,bituminous coal,lignitous coal,industrial semi-coke and bituminous coal based semi-coke as carriers. Their ?ue gas desulfurization activities were evaluated in a ?xed bed system and they were characterized by BET,XRD and FTIR. The results showed that:The desulfurization activities of the adsorbents were mainly provided by the metal oxides from calcination,and the metal ions themselves had no desulfurization activity;The ester groups in the carbon-based carrier were the main factor affecting the desulfurization activity of the metal component,because the ester groups decomposed during calcination process and then metal components were exposed,which improved the desulfurization activity of the adsorbent;The medium metamorphic bituminous coal was a good carrier for preparation of Mn-Ce bimetallic adsorbent,duo to the appropriate amount of ester groups in bituminous coal,which made the metal components uniformly dispersed on the surface of adsorbent.
Mn-Ce bimetallic adsorbents were prepared by ultrasonic assisted pressure impregnation process using carbon-based carriers of anthracite coal,bituminous coal,lignitous coal,industrial semi-coke and bituminous coal based semi-coke as carriers. Their ?ue gas desulfurization activities were evaluated in a ?xed bed system and they were characterized by BET,XRD and FTIR. The results showed that:The desulfurization activities of the adsorbents were mainly provided by the metal oxides from calcination,and the metal ions themselves had no desulfurization activity;The ester groups in the carbon-based carrier were the main factor affecting the desulfurization activity of the metal component,because the ester groups decomposed during calcination process and then metal components were exposed,which improved the desulfurization activity of the adsorbent;The medium metamorphic bituminous coal was a good carrier for preparation of Mn-Ce bimetallic adsorbent,duo to the appropriate amount of ester groups in bituminous coal,which made the metal components uniformly dispersed on the surface of adsorbent.
引文
[1]CARTER L J.Uncontrolled SO2 emissions bring acid rain[J].Science,1979,204(4398):1179-1181.
[2]刘玉香.SO2的危害及其流行病学与毒理学研究[J].生态毒理学报,2007,2(2):225-231.
[3]NEVEUX T,MOULLEC Y L.Wet industrial flue gas desulfurization unit:model development and validation on industrial data[J].Ind Eng Chem Res,2011,50(12):7579-7592.
[4]LI X H,ZHU P,WANG F R,et al.Simultaneous catalytic reductions of NO and SO2 by H2 over nickel-tungsten catalysts[J].J Phys Chem C,2008,112(9):3376-3382.
[5]王建成,刘清雅,肖勇,等.不同活性焦载体对V2O5/A C催化剂脱硫活性的影响[J].燃料化学学报,2011,39(10):776-781.
[6]TSUJI K,SHIRAISHI I.Combined desulfurization,denitrification and reduction of air toxics using activated coke:1.Activity of activated coke[J].Fuel,1997,76(6):549-553.
[7]LIZZIO A A,DEBARR J A.Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char[J].Fuel,1996,75(13):1515-1522.
[8]FANG N J,GUO J X,SHU S,et al.Influence of textures,oxygen-containing functional groups and metal species on SO2 and NO removal over Ce-Mn/NAC[J].Fuel,2017,202:328-337.
[9]韩严和,全燮,薛大明,等.活性炭改性研究进展[J].环境污染治理技术与设备,2003,4(1):33-37.
[10]李远涛,易红宏,唐晓龙,等.Ni-Cu金属氧化物改性活性炭同时脱硫脱硝性能研究[J].工业安全与环保,2017,43(5):4-8.
[11]王晖强,刘明华,林芝,等.ZnFe2O4/AC脱硫剂再生方法的比较[J].化工环保,2018,38(2):207-212.
[12]XING X Y,LIU Z Y,YANG J L.Mo and Co doped V2O5/AC catalyst-sorbents for flue gas SO2 removal and elemental sulfur production[J].Fuel,2008,87(8/9):1705-1710.
[13]ZHANG X Y,ZHENG X R,HAN P,et al.Effects of ultrasound on the desulfurization performance of hot coal gas over Zn-Mn-Cu supported on semi-coke sorbent prepared by high-pressure impregnation method[J].J Energy Chem,2015,24(3):291-298.
[14]朱银惠.煤化学[M].2版.北京:化学工业出版社,2011:89-92.
[15]谢克昌.煤的结构与反应性[M].北京:科学出版社,2002:216-218.
[16]ZHOU J S,HOU W H,QI P,et al.CeO2-TiO2 sorbents for the removal of elemental mercury from syngas[J].Environ Sci Technol,2013,47(17):10056-10062.
[17]张华伟,陈江艳,赵可,等.Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究[J].燃料化学学报,2016,44(4):394-400.
[18]ZHU X B,LIU S Y,CAI Y X,et al.Post-plasma catalytic removal of methanol over Mn-Ce catalysts in an atmospheric dielectric barrier discharge[J].Appl Catal B,2016,183:124-132.
[19]翁诗甫.傅里叶变换红外光谱分析[M].2版.北京:化学工业出版社,2010:308-320.
[2]刘玉香.SO2的危害及其流行病学与毒理学研究[J].生态毒理学报,2007,2(2):225-231.
[3]NEVEUX T,MOULLEC Y L.Wet industrial flue gas desulfurization unit:model development and validation on industrial data[J].Ind Eng Chem Res,2011,50(12):7579-7592.
[4]LI X H,ZHU P,WANG F R,et al.Simultaneous catalytic reductions of NO and SO2 by H2 over nickel-tungsten catalysts[J].J Phys Chem C,2008,112(9):3376-3382.
[5]王建成,刘清雅,肖勇,等.不同活性焦载体对V2O5/A C催化剂脱硫活性的影响[J].燃料化学学报,2011,39(10):776-781.
[6]TSUJI K,SHIRAISHI I.Combined desulfurization,denitrification and reduction of air toxics using activated coke:1.Activity of activated coke[J].Fuel,1997,76(6):549-553.
[7]LIZZIO A A,DEBARR J A.Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char[J].Fuel,1996,75(13):1515-1522.
[8]FANG N J,GUO J X,SHU S,et al.Influence of textures,oxygen-containing functional groups and metal species on SO2 and NO removal over Ce-Mn/NAC[J].Fuel,2017,202:328-337.
[9]韩严和,全燮,薛大明,等.活性炭改性研究进展[J].环境污染治理技术与设备,2003,4(1):33-37.
[10]李远涛,易红宏,唐晓龙,等.Ni-Cu金属氧化物改性活性炭同时脱硫脱硝性能研究[J].工业安全与环保,2017,43(5):4-8.
[11]王晖强,刘明华,林芝,等.ZnFe2O4/AC脱硫剂再生方法的比较[J].化工环保,2018,38(2):207-212.
[12]XING X Y,LIU Z Y,YANG J L.Mo and Co doped V2O5/AC catalyst-sorbents for flue gas SO2 removal and elemental sulfur production[J].Fuel,2008,87(8/9):1705-1710.
[13]ZHANG X Y,ZHENG X R,HAN P,et al.Effects of ultrasound on the desulfurization performance of hot coal gas over Zn-Mn-Cu supported on semi-coke sorbent prepared by high-pressure impregnation method[J].J Energy Chem,2015,24(3):291-298.
[14]朱银惠.煤化学[M].2版.北京:化学工业出版社,2011:89-92.
[15]谢克昌.煤的结构与反应性[M].北京:科学出版社,2002:216-218.
[16]ZHOU J S,HOU W H,QI P,et al.CeO2-TiO2 sorbents for the removal of elemental mercury from syngas[J].Environ Sci Technol,2013,47(17):10056-10062.
[17]张华伟,陈江艳,赵可,等.Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究[J].燃料化学学报,2016,44(4):394-400.
[18]ZHU X B,LIU S Y,CAI Y X,et al.Post-plasma catalytic removal of methanol over Mn-Ce catalysts in an atmospheric dielectric barrier discharge[J].Appl Catal B,2016,183:124-132.
[19]翁诗甫.傅里叶变换红外光谱分析[M].2版.北京:化学工业出版社,2010:308-320.